Process of resolving emulsions



Reissued May 3, 1938 rnooass or RESOLVING env s ons Truman B. Wayne, Houston. Tex.

No Drawing. Original No. 1,919,871, dated July 25, 1933, Serial No. 614,618, May 31, 1932. Ap-

plication for reissue February 14, 1938, Serial 24 Claims.

This invention relates to a process of resolving petroleum emulsions of the character commonly encountered in the production, handling and refining of petroleum. I

The principal object of this invention is to provide an improved process and reagents' for treating petroleum emulsions to separate them into their component parts of oil and water.

This application is, in part, a division of my copending application Serial No. 539,125, filed May 21, 1931; now Patent Number 1,912,330, May 30, 1933.

The present process consists in subjecting a petroleum emulsion of the water and oil type to the action of small proportions of a complex organic condensation product v of high molecular weight, resembling somewhat the synthetic resins produced by the condensation of two or more organic bodies containing resinophore groups selected from the well known. group of compounds known to undergo such reactions, e. g. polyhydric alcohols, aldehydes, aldols, ketones, aromatic hydroxy bodies, unsaturated higher aliphatic acids, cyclic carboxylic acids, primary amines,-amides, and their substituted derivatives.

The new resolving agents disclosed herein are prepared in such a manner that the condensation reactions are not permitted to proceed to the point where water and/or oil insoluble resins are produced. This may be accomplished in various ways as, for example, by retarding the condensation reactions by the presence of an interfering 1 substance, usually a hydrophilic colloid and/or a solvent which increases its or through the substitution of certain grou which prevent the formation of hard, insolubl e' resins, and increase the solubility in water and/or impart a marked hydrotropic efiect to the finished product. :3-

While the herein described series of complex condensation products resemble very closely a modified synthetic resin or plastlcizing agent? they are likewise similar in composition to the more complex dye-stuffs, and may be either acidic or basic,'depending upon the nature and proportions of the various groups introduced, and may be soluble in either water or oil, depending again on the nature of the completed condensation product, andin certain instances may have a pronounced hydrotr'opic eifect and thus possess manypf the propertiesofa mutual solventfo'r My invention contemplates the ,use of a resolv- 5 ing agent having tlie'general characteristics above described, prepared from various combinations of organic groupings produced in various ways. I

attribute the effectiveness of this new type of compound to its high' colloidality, coupled with its very pronounced hydrotropic effect. resulting in a miscibility in water;

very marked action at the interfaces of a'waterin-oil emulsion.

While an attempt will be made to define the course of the various chemical reactions involved stood, however, that the invention is not dependent on any theory herein expressed as to the R I UNITED STATES PATENT oFFwE,-if

course of the reactions or as to the composition of Y the products except as defined in the appended claims. v

As stated above, a composition of the desired properties may be prepared by substituting certain groups in the complex organic condensation products prepared by the reaction of organic compounds containing resinophore groups. For example, the condensation product of synthetic resin type may be modified by the introduction of one or more organic groupings selected from the group comprising .alkyl, cyclo-alkyl, aralkyl, sulfonic, and carboxyl groups. In some instances, the modifying agent may be a detergent body. Specifically, the modifying agent may be an acid selected from the group comprising organic soapforining sulfonic, carboxylic, and sulfo-carboxylic acids, or their salts, esters or amides. Further, modified fatty acids and residues from modified fatty acids may constitute modifying agents. Other specific compounds suitable for use are indicated below and it will be noted that in many instances the final complex condensation product employed as the resolving agent may contain several modifying groupings.

this new type of compound which are set forth above it is to be noted that many of the products are capable of undergoing saponification with alkalis. Moreover, many of the complex condensation products are very stable toward calcium and magnesium salts, and may be successfully used in relatively small proportions on petroleum emulsions which contain natural hard waters in a finely emulsified condition, and which do not readily respond to treatment with the usual commercial resolving compounds based on modified fatty acids, because of the formation of water- 'In'addition to the features which characterize insoluble, oil-soluble calcium and magnesium soaps. I

In accordance with this invention the present process contemplates the resolving of petroleum emulsions by adding thereto a complex condensation product ofthe modified synthetic resin type prepared from a phenolic body and one or more aliphatic bodies containing resinophore groups;

eludes phenol, its homologues, the monocyclic cresols, also dicyclic bodies of the nature of naph thol and its homologues. Diand tri-hydric phenols and many of the poly-hydric hydroxy derivatives of naphthalene and anthracene possess reactive qualities of the same general type,

and are suitable for my purposes. Furthermore,i'; substitution products of the above mentioned types of substances may be used, for instance nitro, chloro, sulfonic, carboxylic, and alkoxy, such as methoxy and ethoxy, derivatives. This class of substances comprises those bodies which may be used as one of the two general classes of reacting substances contemplated in the present invention, and is herein designated as a phenolic body. As will be understood by-jgthose skilled in the art the phenolic bodies ,enumerated. above are all hydroxy aromatic bodies. It

will be further understood that the expression phenolic body includes phthallc anhydride as noted in Example 1, and for the reason that it is a reactive resin-forming acidic substituted aromatic body and has the characteristic of the phenols, enumerated above, required in the preparation of the reaction product of modified synthetic type resins in accordance with my invention.

The aliphatic bodies constituting the second general class or type of reacting substances may be selected from the various polyhydric alcohols, aldehydes, ketones, and higher fatty acids of the aliphatic series and their esters, which are known to undergo resinifying reactions with phenolic bodies and their various derivatives, as set forth above. For instance, aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, or glycerin may be used. Obviously, also, their alkyl ether derivatives such as the monoethyl ether of ethylene glycol, and the ether aliphatic alcohols such as diethylene glycol and their ether derivatives are likewise suitable. Among the suitable aliphatic aldehydes are formaldehyde, acetaldehyde, or butyraldehyde, and their polymerization products. Acetone, methylethylketone, and dipropylketone are some of the suitable aliphatic ketones. The higher fatty acids containing more than eight carbon atoms in the molecule such as ricinoleic, and others, are adapted to my purpose. It is obvious, also, that the esters of these fatty acids with' polyhydric alcohols may be used, as well as the reactive esters of stearic, oleic and linoleic acids.

The modifying agents, aspreviously described, may be organic soap forming acids or their salts, esters or amides. Specific examples of these are stearic, oleic,- linoleic, ricinoleic acids and suitable esters of these fatty acids including castor oil. It will be seen that certain of the esters just enumerated, for instance, castor oil, are aliphatic bodies of the second class possessing resinophore groups, because of the presence of reactive hydroxyl groups in addition to a modifying group and because of the presence of fatty residues within the ester molecule. Obviously, fractional esters of fatty acids such as stearic,

oleic, linoleic, etc., and polyhydric alcohols possess free reactive hydroxyl groups, and areequivalents of castor oil for my purpose.

These substances are well known in the synthetic resin arts and have been employed in the production of the hard, infusible, and insoluble resinoids (synthetic resins) of commerce, which resins are water-repellent and insoluble even if modified to a fluid state. The final products have a high molecular weight. I have discovered that by causing these reactions to proceed under conditions which prevent the formation of resins of the character just described, but more particularly produce water-wettable or soluble reaction products, highly effective demulsifiers for petroleum emulsions may be prepared. This is accomplished by introducing groups which act as modifying agents, under the conditions as previously stated.

The distinguishing structural characteristics of the following reaction products of a phenolic body and one or more chemical individuals of the aliphatic series, are the presence of one or more phenyl, phenylene, naphthyl, or similar groups or residues in intimate association with the corresponding aliphatic residues resulting from the dehydration processes incidental to condensation and polymerization. Furthermore, the process of dehydration may be complicated by more far-reaching transformations, transpositions, or rearrangements of the molecule. The scarcity of analytical data on the resinoids makes any endeavor to accurately delineate their constitution a diflicult matter.

The products prepared and employed in the present invention should not be confused with the simple condensation products prepared by condensing cyclic or poly-cyclic aromatic hydrocarbons with fatty bodies and sulfuric acid at temperatures between 20 and 70 C. Products of this type are classed as sulfo-aromatic compounds of the Twitchell type, and are characterized by the presence of one carboxyl group for each moi. of fatty acid condensed with one moi. of the aromatic body, and one or more sulfonic groups. The condensation is usually effected in a manner which preserves the carboxyl group, and prevents the production of resinous bodies.

In order to illustrate specifically the new type of complex condensation product contemplated for use in accordance with the present invention,

I have set forth below several examples of the type of product suitable for use. However, it is to be understood that I do not confine myself to the specific chemicals, or proportions thereof, set forth in these examples, as it will be readily apparent that equivalents of these specific chemicals and their substituted derivatives, and other proportions,'may be employed without departing from the spirit of the invention or the scope of the appended claims. My broad idea contem plates the formation of condensation products similar to the well known synthetic resins and plastics formed by the condensation reactions between chemical bodies or groups of the character mentioned above, but differing from these insoluble resins in that they are highly colloidal and usually water-soluble as a result of the incorporation therein of organic residues by nuclear substitution and condensation reactions which form complex products of very high molecular weight possessing the desired colloidality and wetting properties.

Example 1 ferred practice the product is prepared by heating 7 together molecular quantities of phthallc acid or its anhydride, diethylene glycol, and oleicacid at 200-210 C. This produces a highly colloidal complex condensation product of the synthetic 7 resin type, which isnothard or insoluble, but

the contrary is'not only in the fluid state but is water wettable. It has the consistency of-a heavy grade of lubricating oil.

The reactions undergone by, phthalic anhydride, a polyhydric alcohol such as diethylene glycl,-and a fatty acid as exemplified by oleic acid inthe above example, may be described as fol lows: The dihydroxy glycol, diethylene glycol,

may first react with phthalic anhydride to form f thehalf ester containing a free hydroxyl and a f'ree' carboxyl group. The remaining hydroxyl E' O P may be "then, esterified by the oleic acid.

One [free carboxyl group still remains on the resin molecule. Since free resin forming carboxyl and 'hydroxyl'groups still remain on the half ester,

I two molecules of the half ester may unite to form fonatedresin of high molecular weight so produced is an active wetting agent, and of great {value in the dehydration of petroleum emulsions a. larger molecule before the oleic acid enters the resin molecule. It is also possible to form initially the half ester of diethylene glycol and oleic acid, and the hydroxy ester thus formed then reacts with the phthalic anhydride. All. of these combinations are possible, and the final product can doubtless represent products of each of these'types of reactions.

This product is, therefore, characterized by the presence of an hydroxy ester derived from a polyhydric alcohol and 'a fatty acid. This product further is characterized by the presence of .a phthalyl residue condensated through a hydrophile carboxyl group with the hydrophile hydrdxyl ground a polyhydric alcohol residue, which is in tuin'mo'dified by a fatty residue. A free hydrophile. (polar) carboxyl group thus remains on the,

product, and the esterlinkages are also hydrophilic in character. The product also has a high molecular weight. The product, therefore, has the properties and characteristics which will cause it to resolve petroleum emulsions.

The thick resin produced maybe sulfonated preferably with an equal volume of chloro-sulfonic acid or oleum at approximately 90-140 C. to render it water soluble. "The material may be freed from its excess of acid by any of the usual methods and used as the acidic mass or in the neutralized. state as a demulsifier for petroleum emulsions.

' Example 2 1- mol. each of anisole (phenyl methyl ether),

formaldehyde in 40 per cent. solution, and oleic acid are heated at 80-100 C. for 2 hours to condense to a resinous material which is cautiously treated at room temperature (20435 c.) with an excess of oleum until water-soluble. The sulwhen'used either as the acidic mass or in the form 01'- its sodium, potassium, or ammonium salt.

Example 3 According to another embodiment of the invention an alkyl phenol is condensed with a ketone, the condensation preferably being effected in the presence of a mineral acid. The resulting prodnot is added to strong sulfuric acid and heated until the mass thickens, whereupon the resulting massis mixed with a fatty acid ester of a polyhydric alcohol and stirred to bring about sulfonation and condensation. The resulting mass is then washed with water to remove the free acid andmay be used as such or may be converted into a water-soluble salt or into an amide or ester.

In the preferredpractice oi. this embodiment of condensed-with a molecular proportion of a ketone, such as acetone, by warming below 100 C.

. in they presence of a small quantity of mineral acid. The condensation may be eii'ected in the' presence of hydrochloric acid at a temperature of 30-40 C. by prolonged standing, or may be more quickly eflecte'd by heating the mass at SIP-70 C. for about four hours. The initial condensation product so formed is then slowly added to an equal volume of 98 per cent. sulfuric acid or oleum and heated at about 100? C. until the mass thickens appreciably. It is then slowly run into 200 parts of a fatty acid ester of a polyhydric alcohol, such as olein, castor oil, or linseed oil, and stirred to sulfonate and condense. The acid mass is then preferably washed with an equal volume of water to remove free mineral acid. The complex water-soluble condensation product so obtained may be used in the dehydration of petroleumemulsions in the form of the acid mass, or may be converted into the corresponding ammonium, sodium, or potassium salt, or into an' amino derivative or ester by combining it with an amine or alcohol, respectively.

.An alternative procedure would be to combine an alkyl-phenol, an aldehyde or'ketone, and a Example 4.

100 parts of the acid condensation product prepared according to Example 3 are condensed with from 100 to 500 parts of b-naphthalene sulfonic acid or a nuclear-substituted aromatic sulfonic acid such as isopropyl naphthalene sulfonic acid,

'- by warming at 80l00 C. The mass is diluted with water until an upper layer separates, which is drawn on and used as a demulsifier in the acid state or converted into its ammonium, sodium, or potassiumsalt, or into an ester by esteriiication with an alcohol, or into an-amino derivative by condensation with an organic base such as dimethylaniline, diethylaniline, triethanolamine, or the like., The demulsifiers of this type are highly-colloidal in water solution, mix readily with oil, and are unusually'efiectlve agents for the resolving of petroleum emulsions.

l ksaniple 5 The waslii i acidic condensation product such as that prepared in accordance with the preceding example may be further condensed with a suitable compound or grouping to provide a resulting water or oil soluble amino derivative. For example, the acid condensation product may be condensed with primary, secondary, or tertiary aliphatic amines or alkyl substituted aromatic amines, which yield water or oil soluble derivatives. In preferred practice I employ an alkyl amine, particularly one which contains one or more hydroxylated aliphatic groups, such as mono-, di-'; or tri-ethanolamine. Products of this type have been found to be unusually effective agents for resolving petroleum emulsions.

As a specific example of this embodiment of the invention, 500 parts of the acid condensation product preparedv according to the method covered in Example 4, which may be freed from its excess of mineral acid by any'well known method,

are combined with 50 parts of diethanolamine;

The reaction between the acidic condensation product and an aromatic primary or secondary amine invloves acylation of the amine through replacement of one or both of the hydrogen atoms of the amino group, .NHz. This is eflected by heating the mixture at elevated temperatures.

In the case of an aliphatic amine, for instance a dialkylamine, the reaction product may be simply the substituted ammonium salt of the R H \l 1 N--SO:-Rz

wherein R and R1 represent alkyl groups, and

.R: is the radical attached to the sulfonic or carboxyl group. This is the ordinary neutralization reaction which does not involve any substitution of the hydrogens attached to the nitrogen. However, acylation of the amine by the acidic condensation product is also possible by heating the mass at elevated temperatures for some time. The substituted ammonium salt undergoes a rearrangement and forms an acylated derivative of theamine while eliminating a molecule of water. This reaction takes place according to the following general scheme:

wherein R is alkyl, R1 is alkyl or H, R: is the radical attached to the sulfonic or carboxyl group, XOH, of the acidic resinoid body, and N is the nitrogen atom.

""{The water solubility of the product is usually increased by condensing the acidic resinoid body with aliphatic amines or aromatic amines containing alkyl groups in the side-chain according to Formula (1), On the other hand, products of the R.R1.N.X.Rz:type indicated in Reaction (2) are very soluble in petroleum products, and form colloidally hydrated aqueous solutions.

Whe .gmuch larger than stoichiometrical proportions'p'f the acidic condensation product are used, a' third type of reaction involving esteriflcation of the hydroxyl groups of the hydroxylated aliphatic amine also occurs. This may occur simultaneously with the acylation of the amino group, and thus provides a very complex condensation product which is a highly eflicient demulsifier for petroleum emulsions. The reaction would then probably take place according to the following general scheme:

wherein R: is the radical attached to the sulfonic or carboxyl group, X.OH, of the acidic resinoid body employed as an acylating agent, and N is the nitrogen atom.

Such condensation products may be exemplifled by the following type formula A.OX.R2

Bax-N A.OX.R3

wherein R2.X is the resinoid radical attached to the nitrogen atom, N; and A.OX.R: is the ester produced by esterification of the hydroxyl groups of the alkyl radical, A.

It is obvious that many permutations and combinations of substances may be prepared from the various reactive bodies known to undergo resiniflcation, and that only a few examples can be given in the specification. It is also obvious that two or more of the resins produced may be further condensed and then combined with a nuclear-substituted aromatic sulfonic acid, and that alkylation and sulfonation can often be conducted simultaneously with resinification in many cases.

Proportions of reacting substances, temperatures, time of heating, etc., are specified in some of the preceding examples while more general directions only are given in others. Obviously, many permutations and combinations in proportions of reacting bodies are made possible by varying the time of heating and/or the temperatures used. For example, if molecular proportions of a phenoloid body and an aldehyde are' heated to a certain temperature for 11. minutes to form a water-soluble condensation product, it is obviousthat if only one-half moi. of aldehyde is' used, the heating must be extended or the temperature raised, or both, to obtain a condensation product of the same physical characteristics. Conversely, if two mols of aldehyde are used either the temperature must be reduced or the time of heating shortened, or both, to prevent the condensation from proceeding to the point where insoluble resins are obtained. The properties of the particular aldehydes, alcohols, fatty acids, etc., used will likewise influence the procedure employed in the preparation of these soluble resinous bodies as will also the nature of the organic residues present substituted derivatives of the various polyhydric alcohols, aldehydes, phenoloid bodies, amines, etc. These various considerations, however; are within the knowledge and practices of the trained organic chemist and will be readily understood by those skilled in the art.

Where reference is made in the appended claims to carboxyl and sulfonic groups it is to be understood that this refers to the presence of COOH and SO2.OH groups respectively, and also to the products formed when they are neutralized by a metallic base, ammonia, or organic amine. Equivalents of these groups are also contemplated.

Where reference is made in the appended claims to phthalic anhydride" it is understood as including phthalic acid. made to a fatty acid, it is understood as including its esters, amides and salts.

The term (resinophore group is used in describing the group or linking within the molecule which is responsible for condensation or polymerization, or both. See Ellis, Synthetic Resins and Their Properties (1923) pages 28, 229, 246, 250, 339.

The term water-wettable as used in the speciflcation and claims refers to the characteristic of the product which enables it to be readily wetted by water and which is usually accompanied by some degree of hydration of the product in contact with the aqueous phase of the'emulsion. When the product segregates at the interface of the emulsion and is adsorbed at the interfacial film wherethe hydrophobe body responsible for the emulsion exists, the water-wettable property of this product counteracts the efiect of the hydrophobe present in the emulsion and thus effects its resolution.

The term water-soluble is usedto include the property of forming colloidally hydrated aqueous solution. From the following paragraph it will be seen that only a limited degree of actual water solubility is necessary for the reagents used for breaking petroleum emulsions, for the reason Where reference is v that extremely small proportions of the reagents are ordinarily used.

The .term oil soluble is used to include the property of colloidal dispersion in the oil phase.

The improved treating agents prepared in accordance with the present invention are used in the proportion of one part of treating agent to form 2,000 to 20,000 parts of petroleum emulsion, either by adding the concentrated product directly to the emulsion or after diluting with water or oil in the conventional manner. The treating agents may be used in any of the numerous ways commonly employed in the treatment of petroleum emulsions as will be apparent.

I do not make any claim to the simpler condensation products of the substituted sulfonic acids such as those produced by treating the latter with aldehydes, polyhydric alcohols, and fatty acids, such as those claimed by other inventors, as many of those involve only the linking of two cyclic or polycyclic groups by means of an aldehyde bridge or a similar condensation reaction.

I claim:

1. The process of resolving water-in-oil emulsions which comprises adding thereto a highly colloidal complex condensation product of the modified synthetic resin type prepared from a phenolic body and one or more aliphatic bodies containing resinophore groups, together with a modifying agent capable of preventing the pro-' duction of a reaction product of the hard, insoluble, synthetic resin type.

2. The process of resolving water-in-oil emul-' sions which comprises adding thereto a highly colloidal complex condensation product of the modified synthetic resin type prepared from a phenolic body and an aliphatic body containing resinophore groups selected from the group comprising polyhydric alcohols, higher fatty acids, and aldehydes of the aliphatic series, together with a modifying agent capable of preventing the production of a reaction product of the hard, insoluble, synthetic resin type.

3. The process of resolving water-in-oil emulsions which comprises adding thereto a highly colloidal complex condensation'product of the modified synthetic resin type prepared from a phenolic body and a polyhydric alcohol, together with a modifying agent, comprising a fatty body, capable of preventing the production of a reacision product of the hard, insoluble, synthetic resn type.

4. The process of resolving water-in-oil emul- 4 sions which comprises adding thereto a highly colloidal complex condensation product of the modified synthetic 'resin type prepared from a reactive resin-forming acidic substituted aromatic body, a polyhydric alcohol and a modifying iatty acid, producing a water-wettable or soluble reaction product.

5. The process of resolving water-in-oil emulsions which comprises adding thereto a highly colloidal complex condensation product of the modified synthetic resin type prepared from phthalic anhydride, a polyhydric alcohol and a. modifying fatty acid, producing a water-wettable or soluble reaction product.

6. The process of resolving water-in-oil emulsions which comprises adding thereto a highly colloidal complex condensation product of the modified synthetic resin type prepared from phthalic anhydride and an ester of a fatty acid with a polyhydric alcohol, producing a waterwettable or soluble reactionprod'uct.

7. The process of resolving water-in-oil emul-.

sions which comprises adding thereto a highly colloidal complex condensation product of the modified synthetic resin type prepared from phthalic anhydride and a. fatty acid ester containing one or more reactive hydroxyl groups,

producing a watcr-wettable product.

8. The process of resolving water-in-oil emulsions which comprises adding thereto a highly colloidal waterwettable' or soluble complex condensation product of the modified synthetic resin type, characterized by the presence of a phthalyl residue condensed with a hydroxy ester derived from a polyhydric alcohol and a fatty acid.

9. The process of resolving water-in-oil emulsions which comprises adding thereto a complex condensation product of the modified synthetic resin type prepared from a phenolic body, one or more aliphatic bodies containing resinophore groups, and a nuclear-substituted aromatic sulfonic acid.

10. The process of resolving water-in-oil emulsions which comprises adding thereto a complex condensation product of the modified synthetic resin type prepared from a. phenolic body, a polyhydric alcohol of the aliphatic series, and a or soluble reaction nuclear-substituted aromatic sulfonic acid.

polyhydric alcohol, an aldehyde of the aliphatic series, and a nuclear-substituted aromatic sulfonic acid.

13. The process of resolving water-in-oil emulsions which-comprises adding thereto a complex condensation product of the modified synthetic resin type prepared from a phenolic body, a polyhydric alcohol, an aldehyde of the aliphatic series, a fatty acid having more than eight carbon atoms, and a nuclear-substituted aromatic sulfonic acid.

14. The process of resolving water-in-oil emulsions which comprises adding thereto a treating agent comprising a water-soluble derivative of the condensation product of a phenolic body, a polyhydric alcohol, and an aromatic compound selected from the group comprising aromatic sulfonic acids and nuclear-substituted derivatives thereof, said water-soluble derivatives being a salt, ester, or amino derivative thereof.

15. The process of resolving water-in-oil emulsions which comprises adding thereto a treating agent comprising a complex condensation product of a phenolic body, a polyhydric alcohol, an aldehyde, and an aromatic compound selected from the group comprising aromatic sulfonic acids and nuclear-substituted derivatives thereof.

16. The process of resolving water-in-oil emulsions which comprises adding thereto a treating agent comprising a water-soluble derivative of the condensation product of a phenolic body, a polyhydric alcohol, an aldehyde, and an aromatic compound selected from the group comprising aromatic sulfonic acids and nuclear-substituted derivatives thereof, said water-soluble derivative being a salt, ester, or amino derivative thereof.

17. The process of resolving water-in-oil emulagent comprising a complex condensation prodan aromatic compound selected from the group comprising aromatic sulfonic acids and nuclear-.- substituted derivatives thereof, said water-soluble derivative being a salt, ester, or amino dcrivative.

19. The process of resolving water-in-oil emulsions which comprises adding thereto a treating agent comprising a complex condensation product of a phenolic body, a polyhydric alcohol, an aldehyde, a fatty acid having more than eight carbon atoms, a nuclear-substituted aromatic sulfonic acid, and an alkylamine containing a hydroxylated aliphatic group.

20'. The process of resolving water-in-oil emulsions which comprises adding thereto the condensation product of an alkyl amine and a res inoid body prepared from a phenolic body and one or more aliphatic bodies containing resinophore groups, together with a modifying agent capable of preventing the production of a reaction product of the hard, insoluble, synthetic resin type.

21. The process of resolving water-in-oil emulsions which comprises adding thereto the condensation product of an alkyl amine and a resinoid body characterized by the presence of one or more aromatic residues from a phenolic body linked with residues from members of the aliphatic series. 7

22. The process of resolving petroleum emulsions which comprises adding thereto a treating agent comprising a water-soluble substituted ammonium salt of the general type R.R1.HN.X.OH.R1 wherein R is alkyl, R1 is alkyl or hydrogen, NH is an imino group, -X. Z)H-is a carboxyl or sulfo group, and R2 is a complex resinoid body, said resinoid body being characterized by the presence of one or more aromatic residues from a phenolic body linked with residues from members 01' the aliphatic series.

23. The process of resolving petroleum emulsions which comprises adding thereto a treating agent comprising an oil-soluble substituted amine of the general type wherein R is alkyl, R1 is alkyl or hydrogen, N is a nitrogen atom, X is a residue from a sulfo or carboxyl group, and R2 is a complex resinoid body, said resinoid body being characterized by the presence of one or more aromatic residues from a phenolic body linked with residues from members of the aliphatic series.

24. The process of resolving petroleum emulsions which comprises adding thereto a treating agent comprising a substituted amine oi the general type A.OX.R:

wherein A.OX.R: is the ester radical produced by esteriflcation of the hydroxyl groups of the alkyl radical or radicals, A, N is a nitrogen atom, and R21! is the residue from the complex resinoid body, R2.X.OH, said resinoid body being characterized by the presence of one or more aromatic residues from a. phenolic body linked withresidues from members of the aliphatic series.

TRUMAN B. WAYNE. 

